US4439528A - Spontaneous opal glass compositions - Google Patents
Spontaneous opal glass compositions Download PDFInfo
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- US4439528A US4439528A US06/500,565 US50056583A US4439528A US 4439528 A US4439528 A US 4439528A US 50056583 A US50056583 A US 50056583A US 4439528 A US4439528 A US 4439528A
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- 239000011521 glass Substances 0.000 title claims abstract description 90
- 239000011022 opal Substances 0.000 title claims abstract description 29
- 230000002269 spontaneous effect Effects 0.000 title claims abstract description 14
- 239000000203 mixture Substances 0.000 title description 15
- 239000003513 alkali Substances 0.000 claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 41
- 239000000377 silicon dioxide Substances 0.000 abstract description 21
- 229910052681 coesite Inorganic materials 0.000 abstract description 19
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 19
- 229910052682 stishovite Inorganic materials 0.000 abstract description 19
- 229910052905 tridymite Inorganic materials 0.000 abstract description 19
- 229910004742 Na2 O Inorganic materials 0.000 abstract description 9
- 229910018404 Al2 O3 Inorganic materials 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 43
- 239000003599 detergent Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 7
- 208000016261 weight loss Diseases 0.000 description 7
- 230000004580 weight loss Effects 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000005191 phase separation Methods 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 3
- 239000006121 base glass Substances 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910004865 K2 O Inorganic materials 0.000 description 2
- 229910011763 Li2 O Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 238000007496 glass forming Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910016264 Bi2 O3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019639 Nb2 O5 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000006066 glass batch Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/005—Compositions for glass with special properties for opaline glass
Definitions
- Opacity in glasses is normally achieved through one of two mechanisms or as a result of a combination of those two mechanisms.
- the first means of light scattering involves the presence of a small amount of material suspended in the glass which has an index of refraction differing very markedly from that of the base glass phase.
- the phases present may differ less in index, but where the suspended phase constitutes a major proportion of the body, the high number of interfaces occurring gives rise to extensive light scattering with consequent opacity.
- Either mechanism may involve suspensions of crystals in a glassy matrix or suspensions comprising two immiscible glassy phases.
- Opal glasses have also been classified by the glass manufacturer according to the method of production. For example, where the kinetics of phase separation are so rapid that opacity occurs during the quick cooling of a glass body characteristic of the conventional glass forming processes, spontaneous opals are stated to result. In contrast, where the kinetics of phase separation are so slow that the glass body must be maintained for a substantial length of time within a temperature interval wherein phase separation takes place at a finite rate, the resultant products are termed reheat or thermally opacifiable opals. As can be readily appreciated, the need for a separate heat treating step significantly increases the production cost of reheat opal glasses.
- the primary objective of the present invention is to provide an opal glass demonstrating a very high degree of opacity suitable for use as dinnerware. That utility impresses several constraints upon the character and means of production of the glass. To illustrate, the operable compositions will form spontaneous opals so that the expense of special heat treating procedures to secure the desired opacity will be eliminated.
- the glass must resist chemical attack by alkalies present in commonly used dishwashing materials. Prolonged and/or repeated exposure of the glass must neither remove the gloss from the surface of the dish nor cause a degree of porosity in the surface which can result in the absorption of foreign substances with consequent staining. Most preferably, the glass will be compatible with currently conventional decorating techniques.
- the crystal liquidus temperature will be less than 1350° C. by as large an increment as possible.
- any inclusion of fluorine will be in small amounts, viz., less than 5% by weight.
- fluorine is relatively volatile and, hence, pollutes the air to a certain extent, it is preferred that the fluorine level be held as low as possible, ideally zero.
- the viscosity of the glass at the liquidus temperature will exceed 200 poises.
- alkaline earth metal silicate glasses can exhibit very dense opacities because of the very broad regions of immiscibility in the binary systems.
- the present invention is founded in my discovery that the addition of zinc to calcium silicate opal glass compositions markedly enhances the chemical durability thereof. Whereas previous researchers have disclosed useful opal glasses containing silica and the alkaline earths, those glasses are unlike the products of the instant invention either because they owe their opacity to calcium fluoride crystals and are not as opaque as the present glasses, or because they contain appreciable amounts of boron and do not display the desired durability.
- compositions yield spontaneous opal glasses of dense opacity, excellent resistance to attack by alkalies such as are found in dishwasher detergents, coefficients of thermal expansion (25°-300° C.) between about 60-90 ⁇ 10 -7 /°C., softening points in excess of 750° C., crystal liquidus temperatures below 1350° C., liquidus viscosities in excess of 200 poises, and wherein the opacity results from spherically-shaped droplets of an immiscible glassy phase having diameters of less than one micron.
- the opacifying agents include one or more of BaO, CaO, CoO, CuO, MgO, MnO, NiO, and ZnO. There is no definition of the character of the opacifying phase; the text merely alludes to diffusing particles.
- U.S. Pat. No. 3,661,601 is directed to the manufacture of spontaneous opal glasses wherein the opacity is caused by the presence of fluoride-containing droplets of an immiscible glassy phase.
- the glasses consist essentially, in weight percent, of:
- Up to 10% total of at least one oxide of the following group may optionally be included: BaO, Bi 2 O 3 , CeO 2 O, GeO 2 , La 2 O 3 , Nb 2 O 5 , P 2 O 5 , PbO, SrO, TiO 2 , and ZnO.
- U.S. Pat. No. 3,681,098 is drawn to the formation of spontaneous opal glasses wherein the opacity is generated through the presence of fluoride-containing droplets of an immiscible glassy phase and CaF 2 crystals.
- the glasses consist essentially, in weight percent, of:
- At least one oxide of the following group may optionally be included: B 2 O 3 , BaO, MgO, P 2 O 5 , PbO, SrO, TiO 2 , ZnO, and ZrO 2 .
- U.S. Pat. No. 4,311,529 discloses the tinting of spontaneous opal glasses wherein CaF 2 crystals constitute the opacifying phase.
- the base glass compositions consist essentially, in weight percent, of:
- RO consists of at least one oxide from the group BaO, CaO, MgO, SrO, and ZnO
- R 2 O consists of at least one oxide from the group of Li 2 O, Na 2 O, and K 2 O.
- CaO comprises at least 60% of the RO content
- Na 2 O comprises at least 75% of the R 2 O content.
- Tables I-XIII report examples of glass compositions, expressed in terms of parts by weight on the oxide basis, illustrating the parameters of the present invention. Inasmuch as the sum of the tabulated components totals or approximately totals 100, for all practical purposes the individual values of the recorded constituents may be deemed to reflect weight percent. In accordance with conventional glass analysis practice, where fluorine was utilized in the glass batch materials, it is recited as the entity, fluoride, since it is not known with which cation it is bonded. Tables IA-XIIIA report the compositions in terms of cation percent. In certain instances comparisons of compositional variations becomes more clear when viewed on a cation basis than on a simple weight percent basis. The actual ingredients for the glass batches may comprise any materials, either oxides or other compounds, which, when melted together, will be converted into the desired oxides in the proper proportions.
- the solution is heated to 95° C. and samples of the glass immersed therein, the surface area of the samples being limited by the ratio of 12 square inches to one pound of the solution.
- the samples are withdrawn from the solution at 24-hour intervals up to 96 hours, rinsed in tap water, and wiped dry. The gloss of each sample was compared visually to reference samples.
- the porosity induced in the glass through attack by the alkalies present in the detergent was determined in the following manner.
- Tables I and IA illustrate spontaneous opal glass compositions in the CaO-Al 2 O 3 -B 2 O 3 -SiO 2 system of the type known to the prior art.
- the weight loss data unequivocally demonstrate the poor resistance to alkalies exhibited by those glasses, thereby rendering them unsuitable for tableware.
- Tables II and IIA reveal that the replacement of SiO 2 by ZnO improves the resistance of calcium silicate opal glasses to attack by alkalies.
- An examination of Examples 11-13 evidences a similar effect in glasses containing Na 2 O. Those Examples also dramatize the profound difference in resistance to alkali attack between replacing SiO 2 with ZnO and replacing SiO 2 with additional CaO.
- Examples 11-13 further illustrate that ZnO does not adversely affect the kinetics of opal information. At high temperatures ZnO appears to suppress phase separation, but during rapid cooling the opal phase "strikes in" at a very convenient temperature.
- Tables III and IIIA manifest that, in spite of its similarity in size and charge to zinc, the inclusion of magnesium does not impart an equal improvement in alkali resistance to the glasses.
- Tables V and VA indicate that high levels of ZnO enhance the resistance of the glasses to alkali attack even at relatively low SiO 2 values. Moreover, in glasses containing such low levels of SiO 2 , ZnO not only improves the alkali resistance thereof but also the density of opacity. Nevertheless, it must be noted that the inclusion of fluoride in glasses of low silica contents deleteriously affects the alkali resistance of such glasses even when high levels of ZnO are present.
- Tables VI and VIA illustrate the flexibility available in adjusting the content of alkali metal and/or alkaline earth metal to increase the coefficient of thermal expansion of the glass with minimal effect upon alkali resistance. For example, a slight increase in the level of CaO at the expense of SiO 2 raises the expansion coefficient with only a slight reduction in alkali resistance. Unfortunately, a concomitant effect is a sacrifice in the density of the opacity. Opal density can be restored, however, through the addition of fluoride. And because of the high SiO 2 contents of the glasses, this addition of fluoride does not have a markedly adverse effect upon alkali resistance.
- Tables VII and VIIA and Tables VIII and VIIIA provide further illustrations of varying the alkali metal contents of the glasses to yield articles of acceptable resistance to alkalies.
- Li 2 O can replace part of the SiO 2 without undue reduction in alkali resistance.
- K 2 O can be utilized as part of the alkali metal content and its use appears to enhance the alkali resistance of the glass. Nevertheless, its effect upon phase separation is very profound such that the restoration of opacity demands greater fluoride levels than are desirable.
- Tables IX and IXA show that replacing CaO with ZnO causes a reduction in the coefficient of thermal expansion of the glass as well as improving the alkali resistance thereof as has been illustrated above.
- Tables X and XA disclose that a small amount of Al 2 O 3 can lead to a marked improvement in alkali resistance.
- a comparison of Example 39 with Example 40 clearly evidences a significant improvement in alkali resistance when Al 2 O 3 is substituted for SiO 2 .
- a similar effect occurs when Al 2 O 3 replaces some SiO 2 and alkali metal oxide, as is demonstrated through a comparison of Example 41 with Example 39.
- Examples 12 and 31 manifest a fivefold reduction in weight loss when Al 2 O 3 is substituted for Na 2 O and CaO, and the SiO 2 value is maintained constant.
- Tables XI and XIA are designed to demonstrate the correlation which exists between the weight loss measurements and the above-described detergent test. Thus, glasses exhibiting a weight loss of 0.08 mg/cm 2 will sometimes demonstrate an "A" rating in the stain test.
- the loss of gloss observed on the top surface of the samples and the retention of gloss seen on the bottom surface of the samples can be explained in the following manner.
- the bottom refers to the surface of the sample which contacts the steel plate onto which the melt is poured to form glass patties. This surface is analogous to and would be expected to manifest properties similar to those noted on the surface of glass articles formed via a pressing operation.
- the top surface cools slowly and is conjectured to have associated with it an exceptionally coarse phase separation.
- Tables XII and XIIA illustrate studies undertaken to investigate means for achieving a lower crystal liquidus temperature in the subject glasses without harming the alkali resistance thereof.
- the exemplary compositions reported demonstrate the effect resulting from mixing the alkaline earth metal oxides. As is evident, any decrease in liquidus temperature attributed to the entropy of mixing, when the alkaline earth metal oxides are combined, is virtually negligible compared to the direct influence of the ionic size of the individual alkaline earth metals. It should also be noted that the viscosity of the glasses tends to become independent of composition at very high temperatures. Consequently, any change in composition which reduces the liquidus temperature automatically increases the viscosity of the glass at the liquidus.
- Example 52 exhibits a desirably low liquidus temperature and high liquidus viscosity but, unfortunately, has unsatisfactory alkali resistance.
- ZnO can be added to improve alkali resistance but, as manifested in Table IV above, ZnO raises the liquidus temperature.
- Tables XIII and XIIIA point out that not only does the substitution of TiO 2 for SiO 2 not reduce the crystal liquidus temperature, but also that the substitution introduces color into the opal glass.
- the replacement of SiO 2 with B 2 O 3 or P 2 O 5 does not appear to endow the final glass with any advantageous properties.
- the more preferred glasses will consist essentially, expressed in terms of weight percent on the oxide basis, of 60-70% SiO 2 , 20-30% CaO, 5-15% ZnO, 1.5-4% Na 2 O, 0-2% Al 2 O 3 , and 0-3% F.
- Example 12 is deemed to be the most preferred composition. Electron micrographs of that glass in the opal state demonstrate that spherical amorphous droplets no larger than about 0.5 micron impart the opacity. Such small droplets will not constitute stress concentrating sites. Inasmuch as the alkali metal content of the inventive glasses is low, products made therefrom are quite useful in microwave applications.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
______________________________________
Description
______________________________________ SiO.sub.2 50-72 CaO 10-40 ZnO 4-40 Na.sub.2 O 0-8 Al.sub.2 O.sub.3 0-2 F 0-5 ______________________________________
______________________________________ SiO.sub.2 66-81 B.sub.2 O.sub.3 10-27 Li.sub.2 O and/or Na.sub.2 O and/or K.sub.2 O 1-7 Al.sub.2 O.sub.3 0-1 Opacifying Agents 3-24 ______________________________________
______________________________________ SiO.sub.2 50-75 Na.sub.2 O 0-7 Al.sub.2 O 3-9 K.sub.2 O 0-7 CaO 11-20 Na.sub.2 O + K.sub.2 O 3-10 B.sub.2 O.sub.3 1-7 F 2-4 ______________________________________
______________________________________ SiO.sub.2 50-75 Al.sub.2 O.sub.3 3-14 CaO 10-20 Na.sub.2 O 0-7 K.sub.2 O 0-7 Na.sub.2 O + K.sub.2 O 3-10 MoO.sub.3 and/or WO.sub.3 and/or As.sub.2 O.sub.3 0.25-5 F 2-5 ______________________________________
______________________________________ SiO.sub.2 57-61 ZnO 8-10 Al.sub.2 O.sub.3 10-11 Na.sub.2 O 8-9 B.sub.2 O.sub.3 1-2 K.sub.2 O 2-2.5 CaO 5-6.5 F 3-4 ______________________________________
______________________________________ SiO.sub.2 60-75 Al.sub.2 O.sub.3 2-7 B.sub.2 O.sub.3 8-15 ZrO.sub.2 0-2.5 RO 9-17 TiO.sub.2 0-4 R.sub.2 O 3-7 F 1-4 ______________________________________
TABLE I ______________________________________ 1 2 3 4 5 6 7 ______________________________________ SiO.sub.2 67.6 68.1 68.5 63.3 62.6 63.0 63.5 Al.sub.2 O.sub.3 6.62 4.44 2.24 8.95 6.64 4.46 2.24 B.sub.2 O.sub.3 1.51 3.03 4.58 3.06 1.51 3.04 4.60 CaO 24.3 24.4 24.6 24.6 29.2 29.4 29.6 mg/cm.sup.2 0.16 0.25 0.37 0.17 0.19 0.25 0.36 ______________________________________
TABLE IA ______________________________________ 1 2 3 4 5 6 7 ______________________________________ SiO.sub.2 65.0 65.0 65.0 60.0 60.0 60.0 60.0 Al.sub.2 O.sub.3 7.5 5.0 2.5 10.0 7.5 5.0 2.4 B.sub.2 O.sub.3 2.5 5.0 7.5 5.0 2.4 5.0 7.5 CaO 25.0 25.0 25.0 25.0 30.0 30.0 30.0 ______________________________________
TABLE II ______________________________________ 8 9 10 11 12 13 ______________________________________ SiO.sub.2 64.5 60.8 57.1 72.9 66.5 67.9 CaO 35.4 35.0 34.6 24.3 23.9 29.3 ZnO -- 4.12 8.14 -- 6.93 -- Na.sub.2 O -- -- -- 2.69 2.64 2.69 mg/cm.sup.2 0.24 0.09 0.06 0.23 0.05 0.24 Op. Liq. -- -- -- 1400 1140 1200 Cry. Liq. -- -- -- 1365 1300 1360 ______________________________________
TABLE IIA ______________________________________ 8 9 10 11 12 13 ______________________________________ SiO.sub.2 63 60 57 70 65 65 CaO 37 37 37 25 25 30 ZnO -- 3 6 -- 5 -- Na.sub.2 O -- -- -- 5 5 5 ______________________________________
TABLE III ______________________________________ 14 15 16 17 ______________________________________ SiO.sub.2 66.3 68.9 66.5 68.9 CaO 23.8 24.7 22.9 23.7 ZnO 6.91 -- 6.92 -- MgO -- 3.55 -- 3.55 Na.sub.2 O 2.50 2.60 2.37 2.46 Al.sub.2 O.sub.3 0.217 0.23 1.30 1.35 mg/cm.sup.2 0.05 0.22 0.01 0.21 ______________________________________
TABLE IIIA ______________________________________ 14 15 16 17 ______________________________________ SiO.sub.2 65.0 65.0 65.0 65.0 CaO 25.0 25.0 24.0 24.0 ZnO 5.0 -- 5.0 -- MgO -- 5.0 -- 5.0 Na.sub.2 O 4.75 4.75 4.5 4.5 Al.sub.2 O.sub.3 0.25 0.25 1.5 1.5 ______________________________________
TABLE IV ______________________________________ 18 19 20 21 ______________________________________ SiO.sub.2 58.2 57.0 58.1 57.0 CaO 12.7 12.5 10.6 10.4 SrO 23.5 23.1 19.6 19.2 ZnO -- -- 6.15 6.03 Na.sub.2 O 2.11 2.07 2.11 2.07 Al.sub.2 O.sub.3 1.15 1.14 1.15 1.14 F 1.95 3.84 1.95 3.84 mg/cm.sup.2 0.42 0.43 0.10 0.08 Cry. Liq. 1300 1325 1334 1370 ______________________________________
TABLE IVA ______________________________________ 18 19 20 21 ______________________________________ SiO.sub.2 62.74 61.54 62.74 61.53 CaO 14.71 14.42 12.26 12.02 SrO 14.71 14.42 12.26 12.02 ZnO -- -- 4.90 4.81 Na.sub.2 O 4.41 4.33 4.41 4.33 Al.sub.2 O.sub.3 1.47 1.44 1.47 1.44 F 1.96 3.85 1.96 3.85 ______________________________________
TABLE V ______________________________________ 22 23 24 ______________________________________ SiO.sub.2 54.2 51.1 53.2 CaO 26.7 12.3 26.1 ZnO 19.0 36.5 18.6 F -- -- 1.96 mg/cm.sup.2 0.10 0.03 0.20 Op. Den. Clear Dense Dense ______________________________________
TABLE VA ______________________________________ 22 23 24 ______________________________________ SiO.sub.2 56.0 56.0 54.9 CaO 29.5 14.5 14.2 ZnO 14.5 29.5 28.9 F -- -- 2.0 ______________________________________
TABLE VI __________________________________________________________________________ 12 25 26 27 28 29 30 __________________________________________________________________________ SiO.sub.2 66.5 64.5 61.6 59.8 65.8 64.7 62.8 CaO 23.9 25.8 28.7 27.9 24.0 24.2 23.5 ZnO 6.93 6.94 6.9 6.7 6.96 7.0 6.8 Na.sub.2 O 2.64 2.64 2.65 2.57 3.18 4.0 3.89 F -- -- -- 2.91 -- -- 2.94 mg/cm.sup.2 0.05 0.07 -- 0.06 0.05 -- 0.06 Op. Den. Dense Dense Clear Dense Medium Light Dense Exp. 67 70 -- 76.1 70 -- 73.2 __________________________________________________________________________
TABLE VIA ______________________________________ 12 25 26 27 28 29 30 ______________________________________ SiO.sub.2 65.0 63.0 60.0 58.3 64.0 62.5 60.7 CaO 25.0 27.0 30.0 29.1 25.0 25.0 24.3 ZnO 5.0 5.0 5.0 4.9 5.0 5.0 4.9 Na.sub.2 O 5.0 5.0 5.0 4.9 6.0 7.5 7.3 F -- -- -- 2.8 -- -- 2.8 ______________________________________
TABLE VII ______________________________________ 31 32 33 ______________________________________ SiO.sub.2 66.5 66.0 65.4 CaO 22.9 24.1 23.3 ZnO 6.92 6.98 7.03 Na.sub.2 O 2.37 1.06 2.41 Li.sub.2 O -- 0.71 0.52 Al.sub.2 O.sub.3 1.30 1.09 1.32 mg/cm.sup.2 0.01 0.05 0.05 Cry. Liq. 1410 1420 1370 Op. Den. Dense Dense Dense ______________________________________
TABLE VIIA ______________________________________ 31 32 33 ______________________________________ SiO.sub.2 65.0 64.0 63.0 CaO 24.0 25.0 24.0 ZnO 5.0 5.0 5.0 Na.sub.2 O 4.5 2.0 4.5 Li.sub.2 O -- 2.75 2.0 Al.sub.2 O.sub.3 1.5 1.25 1.5 ______________________________________
TABLE VIII ______________________________________ 12 34 35 36 ______________________________________ SiO.sub.2 66.5 66.0 68.4 67.5 CaO 23.9 25.1 21.9 23.7 ZnO 6.93 6.88 6.91 6.87 Na.sub.2 O 2.64 1.83 2.63 1.83 mg/cm.sup.2 0.05 0.07 0.06 0.01 ______________________________________
TABLE VIIIA ______________________________________ 12 34 35 36 ______________________________________ SiO.sub.2 65.0 65.0 67.0 66.5 CaO 25.0 26.5 23.0 25.0 ZnO 5.0 5.0 5.0 5.0 Na.sub.2 O 5.0 3.5 5.0 3.5 ______________________________________
TABLE IX ______________________________________ 37 38 35 ______________________________________ SiO.sub.2 67.3 67.8 68.4 CaO 17.8 19.8 21.9 ZnO 12.23 9.6 6.91 Na.sub.2 O 2.59 2.61 2.63 mg/cm.sup.2 0.03 0.04 0.06 Exp. 59.1 60.9 64.1 ______________________________________
TABLE IXA ______________________________________ 37 38 35 ______________________________________ SiO.sub.2 67.0 67.0 67.0 CaO 19.0 21.0 23.0 ZnO 9.0 7.0 5.0 Na.sub.2 O 5.0 5.0 5.0 ______________________________________
TABLE X ______________________________________ 39 40 12 41 31 ______________________________________ SiO.sub.2 65.3 64.0 66.5 64.4 66.5 CaO 19.7 19.8 23.9 19.7 22.9 ZnO 12.25 12.29 6.93 12.26 6.92 Na.sub.2 O 2.59 2.60 2.64 2.34 2.37 Al.sub.2 O.sub.3 -- 1.28 -- 1.28 1.30 mg/cm.sup.2 0.05 <0.01 0.05 0.02 0.01 Op. Liq. -- -- -- -- 1140 ______________________________________
TABLE XA ______________________________________ 39 40 12 41 31 ______________________________________ SiO.sub.2 65.0 63.5 65.0 64.0 65.0 CaO 21.0 21.0 25.0 21.0 24.0 ZnO 9.0 9.0 5.0 9.0 5.0 Na.sub.2 O 5.0 5.0 5.0 4.5 4.5 Al.sub.2 O.sub.3 -- 1.5 -- 1.5 1.5 ______________________________________
TABLE XI ______________________________________ 42 43 44 45 46 47 ______________________________________ SiO.sub.2 62.3 65.0 65.5 64.8 60.0 58.1 CaO 17.9 19.6 19.3 19.1 15.1 10.6 ZnO 6.49 6.77 6.82 6.75 9.37 6.15 Na.sub.2 O 2.22 2.32 1.56 1.54 2.14 2.11 Al.sub.2 O.sub.3 1.22 1.28 1.28 1.27 1.17 1.15 Li.sub.2 O -- -- 0.50 0.50 -- -- MgO -- 0.68 0.68 0.67 -- -- SrO -- 1.72 1.74 1.72 -- 19.6 BaO 9.8 2.56 2.57 2.54 9.42 0.28 F -- -- -- 0.99 2.78 1.95 mg/cm.sup.2 0.08 0.06 0.06 0.06 * 0.10 Stain A A A A A ** Gloss Top Yes Yes Yes Yes No Yes Bottom No No No No No Yes ______________________________________ *Pressed disc. No weight loss data obtained. By analogy to Example 42 estimated to be about 0.05 mg/cm.sup.2. **Test run only 24 hours because of severe loss of gloss.
TABLE XIA ______________________________________ 42 43 44 45 46 47 ______________________________________ SiO.sub.2 65.0 65.0 65.0 64.45 63.11 62.76 CaO 20.0 21.0 20.5 20.3 16.99 12.25 ZnO 5.0 5.0 5.0 4.95 7.28 4.90 Na.sub.2 O 4.5 4.5 3.0 2.97 4.37 4.41 Al.sub.2 O.sub.3 1.5 1.5 1.5 1.49 1.46 1.47 Li.sub.2 O -- -- 2.0 1.98 -- -- MgO -- 1.0 1.0 0.99 -- -- SrO -- 1.0 1.0 0.99 -- 12.25 BaO 4 1.0 1.0 0.99 3.88 -- F -- -- -- 0.99 2.91 1.96 ______________________________________
TABLE XII __________________________________________________________________________ 48 49 50 51 52 53 54 __________________________________________________________________________ SiO.sub.2 67.8 66.3 63.6 65.0 60.1 68.8 62 MgO 0.12 0.10 0.06 0.10 0.05 3.55 0.10 CaO 29.2 23.8 13.7 23.4 13.0 24.7 22.4 SrO -- -- -- 8.63 23.9 0.02 0.02 BaO -- -- -- 0.12 0.34 -- 12.3 ZnO -- 6.91 19.88 -- -- -- -- Na.sub.2 O 2.4 2.37 2.27 2.32 2.15 2.46 2.23 Al.sub.2 O.sub.3 0.44 0.43 0.42 0.42 0.40 0.45 0.41 Cry. Liq. 1380 1430 1475 1347 1245 1415 1290 Viscosity At Liq. 100 80 -- 140 400 100 200 At 1430° C. 65 80 -- 55 52 80 80 S.P. 832 800 786 828 817 825 813 __________________________________________________________________________
TABLE XIIA ______________________________________ 48 49 50 51 52 53 54 ______________________________________ SiO.sub.2 64.9 64.9 64.9 64.9 64.8 65.0 64.9 MgO 0.2 0.1 0.1 0.1 0.1 5.0 0.1 CaO 29.9 25.0 15.0 24.9 15.0 25.0 25.0 SrO -- -- -- 5.0 15.0 -- -- BaO -- -- -- -- 0.1 -- 5.0 ZnO -- 5.0 15.0 -- -- -- -- Na.sub.2 O 4.5 4.5 4.5 4.5 4.5 4.5 4.5 Al.sub.2 O.sub.3 0.5 0.5 0.5 0.5 0.5 0.5 0.5 ______________________________________
TABLE XIII __________________________________________________________________________ 55 56 57 58 59 60 12 __________________________________________________________________________ SiO.sub.2 66.4 61.5 63.9 60.9 60.8 63.4 66.5 CaO 23.8 23.5 23.7 17.8 23.3 24.3 23.9 ZnO 6.92 6.83 6.88 6.45 6.75 7.04 6.93 Na.sub.2 O 2.50 2.47 2.49 2.33 2.44 2.55 2.64 TiO.sub.2 -- 5.36 2.70 2.53 -- -- -- Al.sub.2 O.sub.3 0.22 0.21 0.24 0.20 1.91 0.20 -- BaO -- -- -- 9.72 -- -- -- P.sub.2 O.sub.5 -- -- -- -- 2.36 -- -- B.sub.2 O.sub.3 -- -- -- -- -- 2.41 -- Color White Purple Tan Tan White White White Cry. Liq. 1420 -- 1415 1370 1355 1370 1300 Gloss Top -- -- -- -- Yes* Yes* Yes** Bottom -- -- -- -- Yes* Yes* No __________________________________________________________________________ *Test run only 24 hours because of severe loss of gloss. **Poured patty surface. No loss of gloss with pressed discs.
TABLE XIIIA ______________________________________ 55 56 57 58 59 60 12 ______________________________________ SiO.sub.2 65.0 61.0 62.0 64.0 61.0 61.0 65.0 CaO 25.0 25.0 25.0 20.0 25.0 25.0 25.0 ZnO 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Na.sub.2 O 4.75 4.75 4.75 4.75 4.75 4.75 5.0 TiO.sub.2 -- 4.0 2.0 2.0 -- -- -- Al.sub.2 O.sub.3 0.25 0.25 0.25 0.25 0.25 0.25 -- BaO -- -- -- 4.0 -- -- -- P.sub.2 O.sub.5 -- -- -- -- 2.0 -- -- B.sub.2 O.sub.3 -- -- -- -- -- 4.0 -- ______________________________________
Claims (3)
______________________________________ SiO.sub.2 50-72 Na.sub.2 O 0-8 CaO 10-40 Al.sub.2 O.sub.3 0-2 ZnO 4-40 F 0-5 ______________________________________
______________________________________ SiO.sub.2 60-70 Na.sub.2 O 1.5-4 CaO 20-30 Al.sub.2 O.sub.3 0-2 ZnO 5-15 F 0-3 ______________________________________
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Cited By (7)
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EP0917135A1 (en) * | 1997-06-05 | 1999-05-19 | Hoya Corporation | Substrate for information recording media |
EP0953548A1 (en) * | 1997-07-30 | 1999-11-03 | Hoya Corporation | Method of producing glass substrate for information recording medium |
US6277777B1 (en) | 1999-08-03 | 2001-08-21 | Johns Manville International, Inc. | Boron-free glass composition and filtration media |
DE102005000663A1 (en) * | 2005-01-04 | 2006-11-09 | Schott Ag | Process for clouding a glass, in particular a borosilicate glass and lamps with a haze |
US9240568B2 (en) | 2011-11-10 | 2016-01-19 | Corning Incorporated | Opal glasses for light extraction |
US10505129B2 (en) * | 2016-04-28 | 2019-12-10 | Schott Ag | Method of production of high-refractive thin glass substrates |
CN112251787A (en) * | 2020-08-26 | 2021-01-22 | 西安交通大学 | Preparation method of zinc calcium silicate nano-array bioactive coating |
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0917135A1 (en) * | 1997-06-05 | 1999-05-19 | Hoya Corporation | Substrate for information recording media |
EP0917135A4 (en) * | 1997-06-05 | 1999-12-15 | Hoya Corp | Substrate for information recording media |
EP0953548A1 (en) * | 1997-07-30 | 1999-11-03 | Hoya Corporation | Method of producing glass substrate for information recording medium |
EP0953548A4 (en) * | 1997-07-30 | 1999-12-22 | Hoya Corp | Method of producing glass substrate for information recording medium |
US6277777B1 (en) | 1999-08-03 | 2001-08-21 | Johns Manville International, Inc. | Boron-free glass composition and filtration media |
DE102005000663A1 (en) * | 2005-01-04 | 2006-11-09 | Schott Ag | Process for clouding a glass, in particular a borosilicate glass and lamps with a haze |
DE102005000663B4 (en) * | 2005-01-04 | 2010-08-05 | Schott Ag | Process for clouding a glass, in particular a borosilicate glass, glass tube and its use |
US9240568B2 (en) | 2011-11-10 | 2016-01-19 | Corning Incorporated | Opal glasses for light extraction |
US9496521B2 (en) | 2011-11-10 | 2016-11-15 | Corning Incorporated | Opal glasses for light extraction |
US10505129B2 (en) * | 2016-04-28 | 2019-12-10 | Schott Ag | Method of production of high-refractive thin glass substrates |
CN112194349A (en) * | 2016-04-28 | 2021-01-08 | 肖特股份有限公司 | Method for producing high-refraction thin glass substrate |
CN112251787A (en) * | 2020-08-26 | 2021-01-22 | 西安交通大学 | Preparation method of zinc calcium silicate nano-array bioactive coating |
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